The present invention No. I relates to an efficient method for the preparation of a polyester block copolymer which is excellent in heat resistance and hydrolysis resistance, in which lactones are addition-polymerized onto a crystalline aromatic polyester.
The present invention No. II relates to a method for the preparation of a polyester block copolymer which is excellent in heat resistance and hydrolysis resistance, and which has a higher molecular weight, in which the polyester block copolymer obtained in the present invention No. I is further allowed to react in a solid state.
The present invention No. III relates to a polyester block copolymer composition which is excellent in heat resistance and hydrolysis resistance, color hue, and melt viscosity stability, and a method for the preparation thereof.
The present invention No. IV relates to a polyester block copolymer composition which is excellent in heat resistance under a contact with a metal and a polyvinyl chloride (PVC), and relates to a heat-sensitive body for a heater cable in which polyester block copolymer-based resin is employed.
The present invention Nos. V and VI relate to a polyester block copolymer composition which is excellent in a blow-moldability and heat resistance.
The present invention No. VII relates to a polyester block copolymer composition composed of a crystalline aromatic polyester and lactones, and relates to a method for the preparation thereof, and which is excellent in a blow-moldability and heat resistance.
Prior arts in relation to the present invention Nos. I and II are as follows.
Many polyester block copolymers possesses a mechanical property such as flexibility, and widely enlarge uses such as parts for cars and electric and electronic parts as a thermoplastic elastomer which is excellent in heat resistance and chemical resistance, which contains a crystalline aromatic polyester unit such as a polybutylene terephthalate unit as a hard segment, and in which crystallinity is lowered by combination of a long chain diol with an aromatic dicarboxylic acid in spite of an aliphatic polyether such as a poly(alkyleneoxide) glycol, and/or an aliphatic polyester such as a polylactone and/or a polyester, and an aromatic polyester.
Hitherto, as a technology for giving flexibility to a crystalline aromatic polyester, JP-B-73004116 Official Gazette states a method for obtaining a block copolymer having a elasticity by reaction of a crystalline aromatic polyester with lactones. The method stated herein is a first method which shows that a block copolymer can be obtained by an addition reaction of lactones, however, there is nothing described in relation to an importance of residual unreacted lactone monomers after the above-described reaction and a technical effect, and there is also nothing described in relation to a melting point in the block copolymer obtained.
On the other hand, JP-B-77049037 Official Gazette describes a method for polymerizing lactones under the presence of a crystalline aromatic polyester which is in a solid phase. By descriptions, it is shown that a method in which a reaction is conducted in a melting state has a problem of a remarkable decline in a melting point of the crystalline aromatic polyester, and it can be solved by conducting a reaction under a solid condition.
However, it includes a problem that since it is a reaction at a low temperature, there is required a long time of period in the reaction, and since productivity is worse, and it lacks practicability.
Further, JP-B-96009661, JP-B-93023289, JP-B-93023290, JP-B-95033434, JP-B-94033435, JP-A-05043666, and JP-A-05043667 Official Gazettes all describe a method for allowing to continuously react a crystalline aromatic polyester with lactones, and some of the Gazettes include descriptions including a step for removing unreacted lactones. Removal of the unreacted lactone described herein has an effect for reducing a monomer smell in the polyester block copolymer and, moreover, by conducting a continuous removal operation, it has an effect for further reducing concentration of the unreacted lactones in the polyester block copolymer.
Still further, some of the above-described prior arts describe that there is included a step for conducting a polycondensation reaction in a solid state, and the polycondensation reaction in a solid state has an effect for increasing a solution viscosity of a polyester block copolymer (P1).
However, all of the prior arts only describe that a thermal property such as a melting point of a resin obtained are decided by raw materials to be employed, reaction temperature, reaction time of period, and conditions for removing unreacted lactones, and all the prior arts do not describe a technical concept and a specific method for intentionally improving the thermal property by increasing the amount of the lactones to be introduced and by remaining the amount of the unreacted lactones.
In JP-A-02252729 and JP-A-04072325 Official Gazettes, there is described a method for elevating a melting point of a block copolymer obtained. The JP-A-02252729 Official Gazette describes a method in which there are dissolved a crystalline aromatic polyester and lactones at a lower temperature, and those have an effect for reducing decomposition reaction by heating, however, there is small an effect for preventing a decline of a melting point, further, occasionally, a reaction time of period unpreferably becomes long. Further, the JP-A-04072325 Official Gazette describes that the lactones is partially added in advance in a highly-polymerized state, and elevation of a melting point can be effectively actualized. However, in spite of an inherent low cost in the lactones, the method partially highly-polymerized in advance includes a problem of a fair adverse affection to total profitability.
JP-A-61287922 Official Gazette describes that in a method for the preparation of an elastic polyester by allowing to react a crystalline aromatic polyester with lactones, the method for the preparation of an elastic polyester characterized in that an addition polymerization is conducted by continuously feeding a melted crystalline polyester and lactones into a reaction vessel, and then, those are allowed to react with each other in a solid state.
However, even in the method, there are not shown a technical concept and a specific method, etc., that thermal properties are intentionally elevated by increasing the amount of the lactones and by remaining the amount of unreacted lactones.
As described hereinabove, those have been still insufficient as a method for the preparation of a polyester block copolymer having a high melting point and a high molecular weight.
Prior arts in relation to the present invention No. III are as follows.
However, in relation to the polyester block copolymer composed of a hard segment and a soft segment described in the prior arts for the present invention No. I, an industrially-produced polymer is not sufficient in heat resistance and hydrolysis resistance, and, in the case that it is applied to a melting molding method such as a blow molding and extrusion molding in which a high melt viscosity is required, there has been caused a problem that moldability is worse.
Accordingly, as a method for elevating a heat resistance and hydrolysis resistance in a polyester block copolymer, there have been proposed a variety of methods until now. Further, there are proposed methods simultaneously elevating a melt viscosity in the many proposes. For example, JP-B-77030999 and the above-described JP-B-77049037 Official Gazettes propose a method for increasing a melt viscosity by a solid phase polymerization. However, in the method for increasing a melt viscosity proposed herein, there is required a very long time of period for heating and, further, hydrolysis resistance is not improved at all.
JP-B-91077826 Official Gazette proposes a method for melt-mixing a monofunctional epoxy compound with a bifunctional epoxy compound. By the method, although heat resistance and hydrolysis resistance are elevated, the hydrolysis resistance is not sufficient, an elevation of a melt viscosity is also insufficient.
In order to allow to become sufficient the hydrolysis resistance of the polyester elastomer obtained by the method, it is required that an excessive amount of the epoxy compounds are added, resulting in that a melting point lowers, and viscosity change is large in reheating, and it is problematic in molding stability in the case of conducting a more precise molding process.
JP-B-92021703, JP-B-89052441, and JP-B-86042930 Official Gazettes describe the further addition of a metal salt of a carboxylic acid as an accelerator in a reaction.
However, melt viscosity in resins obtained herein is not still sufficient and, it is anxious that such the addition of the metal salts unpreferably affects to hydrolysis resistance, and it preferably causes to lower a color hue. On the other hand, as a method for improving a melt viscosity stability, JP-B-88031491 Official Gazette proposes a method of addition of an epoxy compound and carboxylic acids. In the method, since there are added the carboxylic acids which change hydrolysis resistance to worse, there must be added a large amount of the epoxy compounds in order to obtain a sufficient hydrolysis resistance, resulting in that there are caused a cost increase and crystallinity lowers.
Prior arts in relation to the present invention No. IV are as follows.
In recent years, there have been employed composite materials of synthetic resins with metals and PVC in many fields including electric cables. The composite materials are molded by an extrusion molding method or a fusing method, and employed in a variety of uses.
As a use of such the materials, there is a heater cable for an electric blanket and an electric carpet in which heat resistance is required.
Structure of the heater cable, as shown in FIG. 1, is composed of a center wire 1, a short wire 2, a heating wire 3, a heat-sensitive body 4, and an outer cover 5. The heat-sensitive body 4 has a function as a fuse.
This functions in order to cut a heater circuit by fusing the heat-sensitive body 4 which fuses at a narrow temperature range when temperature abnormally elevates, and there have been mainly employed a nylon 12 and a nylon 11 until now. Further, a heat-resistible polyester is employed as the center wire 1, PVC is employed as the outer cover 5, and copper and a copper alloy are employed as the short wire 2 and the heater wire 3.
The heater wire composed of the composite materials are often exposed to heat cycles in view of functions thereof and, if the heat-sensitive body 4 is poor in heat resistance, even though exotherm from the heater wire 3 is in a normal range, the heater circuit is occasionally cut or, contrarily, a fusing function does not occasionally work even in the case of abnormal temperature elevation, resulting in that fire accident is occasionally caused.
Heretofore, there have been mainly employed resins such as the nylon 12 and the nylon 11 as the heat-sensitive body 4.
As the resins, although there is employed a resin which is excellent in heat resistance and does not contain an additive, or a resin composition in which a hindered phenol-based stabilizer is mixed to prevent heat deterioration, those include many problems.
Prior arts in relation to the present invention Nos. V, VI, and VII are as follows.
As a method for preparing a polyester block copolymer by allowing to react an aromatic polyester with lactones, there have been known a method (JP-A-48004116 Official Gazette) by allowing to react a crystalline aromatic polyester with a lactone, a method (JP-A-48004115 Official Gazette) by allowing to react a crystalline aromatic polyester with a lactone and to chain-extend by allowing to react an initial copolymer with a multifunctional acylating agent, and a method (the above-described JP-B-77049037 Official Gazette) for polymerizing the lactones in a solid phase under the presence of a crystalline aromatic polyester.
Although the polyester block copolymers obtained by the methods have excellent rubbery elasticity and excellent weatherability, the copolymers are insufficient in heat resistance, and include a drawback that viscosity, extension, and strength remarkably lower by exposing to a high temperature for a long time of period.
Further, the copolymers do not have a strain-hardening property which is an important property in blow-molding, and there cannot be obtained a molded article having uniform thickness.
Therefore, in order to improve heat resistance and moldability of the above-described polyester-type block copolymers, there have been proposed a method (JP-A-58162654 Official Gazette) in which a mono or more functional epoxy compound is mixed, a method (JP-A-59152947 Official Gazette) in which there are formulated a mono or more functional epoxy compound and a metal salt of an aliphatic carboxylic acid, and a method (JP-A-59155458 Official Gazette) in which there are formulated a mono or more functional epoxy compound and an ethylene-carboxylic acid copolymer. However, melt viscosity is relatively low in the compositions obtained in the methods.
There have been problems that because it is difficult to obtain a mutual relationship between a dependence of a melt viscosity upon extension speed and a mixing amount of the metal salt of an aliphatic carboxylic acid, and quality cannot be stabilized, and heat resistance lowers, etc.
Recently, as a method for solving all the problems, although there has been proposed a method (JP-A-07331046 Official Gazette) in which there are formulated two or more functional epoxy compounds and an imidazole compound, a dependence of a melt viscosity upon extension speed (It is called a strain-hardening property, that is, it is a characteristic of viscosity increase with an increase of an extending speed. Accordingly, a larger hardening property prevents an excessive extension of an extended portion in blow molding owing to a larger viscosity, and an unextended portion is extended owing to a lower viscosity, as a result, uniform thickness is obtained.) is still insufficient. and there cannot be obtained a molded article having uniform thickness in blow molding and, further, there has been a problem that discoloration is remarkable.
Purpose of the present invention No. I is to provide a method for the preparation of a polyester block copolymer from a crystalline aromatic polyester and, specifically, to provide a method for the preparation of a polyester block copolymer which has a low crystallinity and a high melting viscosity and which is excellent in heat resistance, processability, and hydrolysis resistance.
The present inventors, as a result of an investigation of a method for the preparation of a polyester block copolymer which is excellent in heat resistance, processability, hydrolysis resistance, and a high melt viscosity, found out that in the method for the preparation of a polyester block copolymer (P1) by allowing to react a crystalline aromatic polyester (A1) with lactones, thermal characteristics of the polyester block copolymer (P1) can be improved by controlling an introducing amount of lactones (B) with respect to the above-described crystalline aromatic polyester (A1) and an amount of unreacted lactones remained in the polyester block copolymer (P1), and the present invention No. I has been completed.
Purpose of the present invention No. II is to provide a method for the preparation of a high molecular weight polyester block copolymer from a crystalline aromatic polyester and, specifically, to provide a method for the preparation of a polyester block copolymer which is low in crystallinity, and which is excellent in heat resistance, processability, hydrolysis resistance, and which has a high melt viscosity and a higher molecular weight.
The present inventors, as a result of an investigation of a method for the preparation of a polyester block copolymer in which crystallinity is lowered in a crystalline aromatic polyester, and which is excellent in heat resistance, processability, hydrolysis resistance, and which has a high melt viscosity, found out that in the method for the preparation of a polyester block copolymer (P1) by allowing to react the crystalline aromatic polyester with lactones, thermal characteristics of the polyester block copolymer (P1) can be improved by controlling an introducing amount of unreacted lactones remained in the polyester block copolymer (P1) obtained by the reaction and a polyester block copolymer (Pxe2x80x21) obtained through a reaction in a solid phase can be more highly-polymerized, and the present invention No. II has been completed.
Purpose of the present invention No. III is to provide a polyester block copolymer composition and a method for the preparation thereof, which is excellent in heat resistance, hydrolysis resistance and color hue, and which has a high melt viscosity and melt viscosity stability, and which is appropriate in molding processing.
The present inventors, as a result of an intensive investigation for obtaining a resin composition which is excellent in heat resistance and hydrolysis resistance and a polyester block-based copolymer which has a high melt viscosity and a melt viscosity stability and which is appropriate in molding processability, have found that the above-described problems can be solved by heating under a specified condition after mixing a mono or more functional epoxy compound with the polyester block copolymer, and the present invention No. III has been completed.
Purpose of the present invention No. IV is to solve a problem that thermal deterioration is accelerated and heat resistance becomes insufficient by a combined action of a produced copper ion with a covered PVC or hydrochloric acid isolated from the covered PVC because the above-described heater cable is exposed to heat cycles and temperature elevates to approximately 100xc2x0 C. or so, and the heat-sensitive body such as a nylon 12 and nylon 11 is brought into contact with copper or a copper alloy which is a short wire or a heating wire, and those are brought into contact with a PVC cover at a clearance between wound short wires.
The present inventors, as a result of an intensive investigation for solving the problems in the prior arts, have found out that a polyester block copolymer composition is not apt to be suffered by a combined thermal deterioration even under a circumstance in which it is brought into contact with a metal such as copper and copper alloy and PVC, the composition is excellent in heat resistance and hydrolysis resistance, the composition is obtained by allowing to react a polyester copolymer with an epoxy compound after mixing a polyester block copolymer with a specified epoxy compound and a metal complex and heating and kneading, and the present invention No. IV has been completed.
Purpose of the present invention Nos. V, VI, and VII is to provide a polyester block copolymer composition which has an excellent moldability, excellent heat resistance, and rubbery elasticity, and which can be applied to a variety of molding such as blow molding without any problems.
The present inventors, as a result of an intensive investigation, have found out that a polyester block copolymer composition can solve the above-described problems by an elevated strain-hardening property, and the present invention Nos. V and VI have been completed. The polyester block copolymer composition is obtained by mixing a polyester block copolymer with an epoxy compound, and then, heating and kneading. The polyester block copolymer is obtained by copolymerizing through adding a multifunctional compound having three or more carboxylic groups or hydroxyl groups while allowing to react a crystalline aromatic polyester with lactones.
The present inventors have found out that a polyester block copolymer composition can solve the above-described problems by an elevated strain-hardening property, and the present invention No. VII have been completed. The polyester block copolymer composition is obtained by adding an epoxy compound to a polyester block copolymer and heating in a solid phase. The polyester block copolymer is obtained by adding a specified amount of an aliphatic or aromatic multifunctional compound having a specified multifunctional group while allowing to react a crystalline aromatic polyester with lactones.
That is, the present invention No. 1 relates to a method for the preparation of a polyester block copolymer (P1) characterized in that in the method for the preparation of 100% by weight of the polyester block copolymer (P1) by allowing to react A% by weight of a crystalline aromatic polyester (A1) with B% by weight of lactones (B) (proviso that A+B=100), not less than (B+0.5)% by weight of lactones (B) are introduced into A% by weight of a crystalline aromatic polyester (A1), and not less than 0.5% by weight of unreacted lactones are remained with respect to 100% by weight of the polyester block copolymer (P1) after preparation of the copolymer.
The present invention No. 2 relates to a method for the preparation of a polyester block copolymer (P1) as described in the present invention No. 1, in which not less than (B+2.5)% by weight of the lactones (B) are introduced and not less than 2.5% by weight of unreacted lactones are remained with respect to 100% by weight of the polyester block copolymer (P1) after preparation of the copolymer.
The present invention No. 3 relates to a method for the preparation of a polyester block copolymer (P1) as described in the present invention No. 1 or 2, in which reaction proportion (A)/(B) of the crystalline aromatic polyester (A1) with respect to the lactones (B) is 95/5-20/80.
The present invention No. 4 relates to a method for the preparation of a polyester block copolymer (P1) as described in any one of the present invention Nos. 1-3, in which the unreacted lactones are removed from the polyester block copolymer (P1) after reaction.
The present invention No. 5 relates to a method for the preparation of a polyester block copolymer (P1) as described in any one of the present invention Nos. 1-4, in which the unreacted lactones are continuously removed.
The present invention No. 6 relates to a method for the preparation of a polyester block copolymer (P1) as described in any one of the present invention Nos. 1-5, in which the crystalline aromatic polyester (A1) and the lactones (B) are continuously supplied into a reaction vessel and allowed to addition-polymerize, and the polyester block copolymer (P1) is continuously taken out.
The present invention No. 7 relates to a method for the preparation of a polyester block copolymer (P1) as described in any one of the present invention Nos. 1-6, in which the crystalline aromatic polyester (A1) is a polybutylene terephthalate.
The present invention No. 8 relates to a method for the preparation of a polyester block copolymer (P1) as described in any one of the present invention Nos. 1-7, in which the lactones (B) are caprolactone.
The present invention No. 9 relates to a method for the preparation of a polyester block copolymer (Pxe2x80x21) having a high molecular weight characterized in that after having prepared the polyester block copolymer (P1) as described in any one of the present invention Nos. 1-8, it is further allowed to react in a solid phase.
The present invention No. 10 relates to a method for the preparation of a polyester block copolymer (Pxe2x80x21) having a high molecular weight as described in the present invention No 9, in which reaction in a solid phase is continuously conducted.
The present invention No. 11 relates to a polyester block copolymer composition (R) obtained by thermally-processing a polyester block copolymer composition (Q) obtained by melt-mixing 100 parts by weight of a polyester block copolymer (P) with 0.1-5 parts by weight of an epoxy compound (C) having,one or more epoxy groups under an inert gas atmosphere and not less than 120xc2x0 C. in a solid phase, and further, at a temperature lower than a melting point of the polyester block copolymer composition (R) obtained.
The present invention No. 12 relates to a polyester block copolymer composition (R) as described in the present invention No. 11, characterized in that the polyester block copolymer (P) is a polyester block copolymer (P1) obtained by allowing to react a crystalline aromatic polyester (A1) with lactones (B).
The present invention No. 13 relates to a polyester block copolymer composition (R) as described in the present invention No. 11, characterized in that the polyester block copolymer (P) is a polyester block copolymer (P2) obtained by a polycondensation and/or ring-opening polymerization of monomer components constructing a crystalline aromatic polyester (A1); monomer components constructing a low crystalline polyester (A4); an aliphatic polyether (A2); and/or polylactone (A3).
The present invention No. 14 relates to a polyester block copolymer composition (R) as described in any one of the present invention Nos. 11-13, characterized in that the epoxy compound (C) is an epoxy compound (C2) having two or more epoxy groups.
The present invention No. 15 relates to a polyester block copolymer composition (R) as described in any one of the present invention Nos. 11-14 which is obtained by thermally-processing the polyester block copolymer composition (Q) at not less than 150xc2x0 C. and, moreover, at a temperature of 100- to 5xc2x0 C.-lower than a melting point of the polyester block copolymer composition (R).
The present invention No. 16 relates to a polyester block copolymer composition (R) as described in any one of the present invention Nos. 11-15 which is obtained by further thermally-processing the polyester block copolymer composition (Q) after preheating at a temperature less than a melting point of the polyester block copolymer composition (R) and, moreover, at a temperature of not more than 150xc2x0 C. The present invention No. 17 relates to a polyester block copolymer composition (R) as described in any one of the present invention Nos. 11-16 in which there are formulated at least one kind of compounds selected from the group consisting of a hindered phenol-based compound, a sulphur-based compound, a phosphorus-based compound, a phenyl amine-based compound, and a hindered amine-based compound.
The present invention No. 18 relates to a polyester block copolymer composition (R) as described in any one of the present invention Nos. 11-17, in which an acid value is not more than 0.5 mgKOH/g in the polyester block copolymer composition (R) and, moreover, a melting point (Tm(R)) of the composition (R) is not less than a 10xc2x0 C.-lower temperature than a melting point (Tm(P)) of the polyester block copolymer (P) which is a raw material.
Tm(P)xe2x88x9210xc2x0 C.xe2x89xa6Tm(R)
The present invention No. 19 relates to a polyester block copolymer composition (R) as described in any one of the present invention Nos. 11-18, in which a melt viscosity stability (MI(T, P, t+10)/(MI(T, P, t)) is 0.5-2.0 in the polyester block copolymer composition (R).
In the formula, the melt index (MI(T, P, t)) value is a value measured at a heating temperature (T), loading (P), and heating time of period (t) based on a method described in JIS K7210. Herein, T is a temperature higher than a 5xc2x0 C.-higher temperature than a melting point of the composition (R) and, it is a minimum temperature of experimental temperatures described in Table 1 of the JIS K7210, and P is a value selected as ranging in 1-30 g/10 minutes in the MI value. The MI(T, P, t+10) is a value in which the heating time of period is t+10 minutes in conditions of the T and P.
The present invention No. 20 relates to a method for the preparation of a polyester block copolymer composition (R) characterized in that there is thermally-treated a polyester block copolymer composition (Q) in which 100 parts by weight of a polyester block copolymer (P) is thermally mixed with 0.1-5 parts by weight of an epoxy compound (C) having at least one epoxy groups under an inert gas atmosphere and at not less than 120xc2x0 C. in a solid phase and a temperature less than a melting point of the obtained polyester block copolymer composition (R).
The present invention No. 21 relates to a polyester block copolymer composition which comprises thermally-mixing 100 parts by weight of a polyester block copolymer (P1) obtained by a reaction of a crystalline aromatic polyester (A1) and lactones (B) with 0.5-5.0 parts by weight of a mono or morefunctional epoxy compound (C) and 0.01-3.0 parts by weight of a complex-formable agent for a metal (G).
The present invention No. 22 relates to a polyester block copolymer composition as described in the present invention No. 21, characterized in that the crystalline aromatic polyester (A1) is a polyester of an aromatic dicarboxylic acid which is an essential acid component (a) and an aliphatic dicarboxylic acid and/or a cycloaliphatic dicarboxylic acid which are optionally added with an aliphatic diol, an aromatic diol, and/or a cycloaliphatic diol which are a diol component (b).
The present invention No. 23 relates to a polyester block copolymer composition as described in the present invention No. 21, in which the crystalline aromatic polyester (A1) contains not less than 50% by weight of total of butylene terephthalate and ethylene terephthalate units.
The present invention No. 24 relates to a polyester block copolymer composition as described in any one of the present invention Nos. 21-23, in which a copolymerization proportion (A1/B) of the crystalline aromatic polyester (A1) with the lactones (B) is 97/3-50/50 by weight.
The present invention No. 25 relates to a polyester block copolymer composition as described in any one of the present invention Nos. 21-24, in which the epoxy compound (C) is a glycidyl type epoxy compound, a compound shown by any one of general formulae (I)-(V) described below, and a mixture thereof. 
(in the formulae, R1, R2, R3 are an alkyl group and, at least one of those are a methyl group, and total thereof is 8 pieces. Further, xe2x80x9cnxe2x80x9d is 0-5.) The present invention No. 26 relates to a polyester block copolymer composition as described in any one of the present invention Nos. 21-25, in which the complex-formable agent for a metal (G) is at least one kind selected from the group consisting of an oxalic acid derivative, a salicylic acid derivative, and a hydrazide derivative.
The present invention No.27 relates to a heat-sensitive body for a heater cable composed of a polyester block copolymer composition as described in any one of the present invention Nos. 21-26.
The present invention No. 28 relates to a polyester block copolymer composition which comprises, in obtaining the polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A1) with the lactones (B), adding and thermally-kneading 0.5-5.0 parts by weight of an epoxy compound (C) having one or more pieces of epoxy groups (including at least 0.2 part by weight of two or more functional epoxy compound) and 0-2.0 parts by weight of a carbodiimide compound (E) to 100 parts by weight of a polyester block copolymer (P3) obtained by allowing to react 0.1-100% by mol at least three pieces of at least one kind of a multifunctional compound (D) having at least three pieces of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A1).
The present invention No. 29 relates to a polyester block copolymer composition which comprises, in obtaining the polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A1) with the lactones (B), adding and thermally-kneading 0.1-5.0 parts by weight of at least one kind of an epoxy compound (C) having one or more pieces of epoxy groups and 0-2.0 parts by weight of a carbodiimide compound (E) to 100 parts by weight of a polyester block copolymer (P3) obtained by allowing to react 0.1-200% by mol of at least one of a multifunctional compound (D) having at least three pieces of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A1).
The present invention No. 30 relates to a polyester block copolymer composition as described in the present invention No. 28 or 29, in which the crystalline aromatic polyester (A1) is a polyester of an aromatic dicarboxylic acid which is an essential acid component (a) and an aliphatic dicarboxylic acid and/or a cycloaliphatic dicarboxylic acid which are optionally added with an aliphatic diol, an aromatic diol, and/or a cycloaliphatic diol which are a diol component (b).
The present invention No. 31 relates to a a polyester block copolymer composition as described in any one of the present invention Nos. 28-30, in which the crystalline aromatic polyester (A1) contains not less than 50% by weight of total of butylene terephthalate and/or ethylene terephthalate units.
The present invention No. 32 relates to a polyester block copolymer composition as described in any one of the present invention Nos. 28-30, in which a copolymerization proportion of the crystalline aromatic polyester (A1) with the lactones (B) is the same proportion as described in the present invention No. 24.
The present invention No. 33 relates to a polyester block copolymer composition as described in any one of the present invention Nos. 29-32, in which at least one kind of the multifunctional compound (D) contains carboxylic group (i) or an ester-formable group therefrom.
The present invention No. 34 relates to a polyester block copolymer composition as described in any one of the present invention Nos. 28-33, in which the epoxy compound (C) is the same compound as described in the present invention No. 25.
The present invention No. 35 relates to a polyester block copolymer composition as described in any one of the present invention Nos. 28-34, which is employed for blow molding.
The present invention No. 36 relates to a polyester block copolymer composition (R) which comprises, in obtaining the polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A1) with the lactones (B), heating a polyester block copolymer composition (Q) in a solid phase, and the composition (Q) is obtained by formulating and melt-mixing 0.1-5.0 parts by weight of an epoxy compound (C) having one or more pieces of epoxy groups with 100 parts by weight of a polyester block copolymer (P) obtained by allowing to react 0.1-200% by mol of at least one kind of a multifunctional compound (D) having at least three pieces of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A).
The present invention No. 37 relates to a polyester block copolymer composition (R) as described in the present invention No. 36, in which the multifunctional compound (D) contains at least one of carboxylic group (i) or an ester-formable group therefrom.
The present invention No. 38 relates to a polyester block copolymer composition (R) as described in the present invention No. 36 or 37, in which the epoxy compound (C) contains at least one kind of a bifunctional epoxy compound.
The present invention No. 39 relates to a polyester block copolymer composition (R) as described in any one of the present invention Nos. 36-38, in which the polyester block copolymer composition (R) has an acid value of not more than 0.5 mgKOH/g and, moreover, a melting point Tm(R) is not more than a temperature of 5xc2x0 C.-lower than a melting point Tm(P) of the polyester block copolymer (P) before adding the epoxy compound, that is, Tm(R)xe2x89xa7Tm(P)xe2x88x925xc2x0 C.
The present invention No. 40 relates to a polyester block copolymer composition as described in any one of the present invention Nos. 36-39, in which a melt viscosity stability (MIxe2x88x92B)/(MIxe2x88x92A) is 0.5-2.0 which is calculated from an MI value (MIxe2x88x92A) in the polyester block copolymer composition (R) and an MI value (MIxe2x88x92B) after heating for 10 minutes at a temperature selected so as to be a lower temperature in the temperature described in JIS K7210 which is a temperature of 5xc2x0 C.-higher than Tm(R).
The present invention No. 41 relates to a polyester block copolymer composition as described in any one of the present invention Nos. 36-40, which is a composition for blow molding.
The present invention No. 42 relates to a method for the preparation of a polyester block copolymer composition (R) characterized in that in obtaining the polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A) with the lactones (B), there is heated a polyester block copolymer composition (Q) in a solid phase, and the composition (Q) is obtained by formulating and melt-mixing 0.1-5.0 parts by weight of an epoxy compound (C) having one or more pieces of epoxy groups with 100 parts by weight of a polyester block copolymer (P) obtained by allowing to react 0.1-200% by mol of at least one of a multifunctional compound (D) having at least three pieces of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A).
The present invention No. 43 relates to a method for the preparation of a polyester block copolymer as described in the present invention No. 42, in which heating is conducted in a solid phase at conditions of from a temperature lower than a melting point in a solid phase of the polyester block copolymer composition (R) to a temperature higher than a glass transition temperature under an inert gas atmosphere and, moreover, heating is conducted at a temperature (Ta) higher than 120xc2x0 C.
Tg less than Ta less than Tm(R),
and
120xc2x0 C. less than Ta
The present invention No. 44 relates to a method for the preparation of a polyester block copolymer as described in the present invention No. 42, in which the temperature heating in a solid phase is 100- to 5xc2x0 C. -lower than a melting point in a solid phase of the polyester block copolymer composition (R) and, moreover, heating is conducted at a temperature (Ta) higher than 150xc2x0 C.
Tm(R)xe2x88x92100xc2x0 C.xe2x89xa6Taxe2x89xa6Tm(R)xe2x88x925xc2x0 C.,
and
150xc2x0 C.xe2x89xa6Ta
The present invention No. 45 relates to a method for the preparation of a polyester block copolymer as described in any one of the present invention Nos. 42-44, in which heating is conducted in a solid phase at conditions of,
(1) a temperature ranges from a temperature lower than a melting point of the polymer to a temperature higher than a glass transition temperature in a solid phase and, moreover, preheating is conducted at a lower temperature than 150xc2x0 C. and a temperature (Tb) lower than Ta, and then,
(2) a temperature ranges from a temperature lower than a melting point of the polymer to a temperature higher than a glass transition temperature in a solid phase and, moreover, heating is conducted at a temperature higher than 120xc2x0 C.,
Preheating temperature Tb
Tg less than Tb less than Tm(R),
Tb less than 150xc2x0 C.,
and
Tbxe2x89xa6Ta
Heating temperature Ta
Tg less than Ta less than Tm(R),
and
120xc2x0 C. less than Ta